Double-dosage-form etching solution composition

Abstract

The invention relates to the technical field of etching liquid, in particular to a double-dosage-form etching liquid composition. Comprising a main agent and an auxiliary agent, and the main agent comprises the following components in percentage by weight: 8-20% of hydrogen peroxide, 1-10% of a first etching agent, 1-10% of a first inhibitor, 0.1-5% of a first stabilizer and the balance of deionized water; the auxiliary agent comprises 5-30% of a second etching agent, 0.1-5% of a second inhibitor, 1-10% of a chelating agent, 10-40% of a second stabilizer and the balance of deionized water; the first etching agent comprises organic acid and inorganic acid, and the organic acid comprises succinic acid. The etching solution disclosed by the invention shows excellent etching performance, and has good compatibility performance for three-layer film (MTD / Cu / MoNb) and two-layer film (Cu / MoNb) and for different copper thicknesses (3500 / 6000 / 8000).

Description

Technical Field

[0001] The invention relates to the technical field of etching solutions, and in particular to a dual-component etching solution composition. Background Art

[0002] In the panel industry, etching is an indispensable process, and wet etching has been widely used for a long time due to its advantages such as fast etching speed, high selectivity and simple process. The existing technology only meets the etching characteristics of Cu / MoNb single film, and for high Mo alloys, the life is generally not high; for MTD / Cu / MoNb film, it generally contains fluorine, which affects the etching effect and is harmful to the environment and human body; the existing technology is difficult to be compatible with the two, or different film thicknesses, and often has etching defects such as second-segment corners, chamfers, cracks, top verticality, metal residues, etc.

[0003] Chinese invention patent CN116536666A discloses an etching liquid composition, comprising the following components: an oxidant, a fluoride ion source, a metal chelating agent, an etching regulator, a pH regulator and water; the etching regulator comprises carbon heterocyclic compounds and salts thereof and inorganic acids and salts thereof; the etching liquid composition is suitable for etching of different metals and metal oxides, can stably control the etching structure of metal oxides, and the bottom cone angle structure formed by etching is complete, but fluorine has irreversible destructive effect on the bottom metal of the substrate and the etching machine. Summary of the invention

[0004] The invention provides a dual-component etching liquid composition, comprising a main agent and an auxiliary agent, wherein the main agent comprises, by weight percentage, 8-20% of hydrogen peroxide, 1-10% of a first etching agent, 1-10% of a first inhibitor, 0.1-5% of a first stabilizer, and the balance is made up of deionized water; the auxiliary agent comprises 5-30% of a second etching agent, 0.1-5% of a second inhibitor, 1-10% of a chelating agent, 10-40% of a second stabilizer, and the balance is made up of deionized water; the first etching agent comprises an organic acid and an inorganic acid, and the organic acid comprises succinic acid.

[0005] Optionally, the main agent includes, by weight percentage: 8-18% hydrogen peroxide, 1-6% first etchant, 1-6% first inhibitor, 0.1-3% first stabilizer, and deionized water makes up the balance; the auxiliary agent includes 5-20% second etchant, 0.1-5% second inhibitor, 2-7% chelating agent, 20-40% second stabilizer, and deionized water makes up the balance.

[0006] The organic acids also include malic acid and malonic acid.

[0007] The weight ratio of malonic acid, malic acid and succinic acid is (0.8-1.2):(0.5-1):1.

[0008] Optionally, the weight ratio of malonic acid, malic acid and succinic acid is (0.8-1):(0.5-0.8):1.

[0009] The organic acid also includes malic acid and malonic acid, and the weight ratio of malonic acid, malic acid and succinic acid is limited to (0.8-1.2): (0.5-1): 1, which is compatible with the etching of Cu / MoNb film and MTD / Cu / MoNb film. Malonic acid has better complexing ability for specific metals (such as Mo / Nb) due to its stronger acidity. Malic acid is rich in more carboxyl groups and can be used to supplement the complexing ability, especially playing a key role in the etching of Cu. Succinic acid may be used to balance pH and stabilize the complex, and the joint action can stabilize the etching process. For Cu / MoNb film, Cu may be preferentially complexed by malic acid, and Mo / Nb is dissolved by the combined action of malonic acid and succinic acid; for MTD / Cu / MoNb film, the etching of MTD depends on the targeted dissolution of Mo / Nb by a higher concentration of malonic acid, while malic acid and succinic acid maintain the overall complexing balance.

[0010] The weight ratio of the organic acid to the inorganic acid is (4-8):(0.1-0.2).

[0011] Optionally, the weight ratio of the organic acid to the inorganic acid is (5-7): (0.1-0.2).

[0012] The inorganic acid includes at least one of sulfuric acid, nitric acid and phosphoric acid.

[0013] The first inhibitor and the second inhibitor are both selected from at least one of heterocyclic aromatic compounds and heterocyclic aliphatic compounds.

[0014] The heterocyclic aromatic compound includes at least one of furan, thiophene, pyrrole, tetrazole, 5-aminotetrazole, 5-aminotetrazole, 3-amino-1,2,4-triazole, 5-methyltetrazole, and methyltetrazole.

[0015] The heterocyclic aliphatic compound includes at least one of piperazine, methyl piperazine, hydroxyethyl piperazine, pyrrolidine and alloxan.

[0016] The second etchant includes at least two of acetic acid, formic acid, butyric acid, citric acid, glycolic acid, oxalic acid, malonic acid, malic acid, valeric acid, propionic acid, tartaric acid, gluconic acid, succinic acid, and fumaric acid.

[0017] The first stabilizer includes an organic base, and the organic base includes at least one of phenylenediamine, dimethylaminopropylamine, isopropanolamine, diethanolamine, and triisopropanolamine.

[0018] The first stabilizer further comprises at least one of phenylurea, allyl urea, 1,3-dimethylurea, thiourea urea stabilizer and ether stabilizer.

[0019] The urea stabilizer includes at least one of phenyl urea, allyl urea, and 1,3-dimethyl urea.

[0020] The ether stabilizer includes at least one of ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether and diethylene glycol monoisobutyl ether.

[0021] The chelating agent includes at least one of glycine, iminodiacetic acid, alanine, glutamine, asparagine, lysine and arginine.

[0022] The second stabilizer includes at least one of phenolsulfonic acid, naphthalenesulfonic acid, p-toluenesulfonic acid, cresolsulfonic acid, dodecylbenzenesulfonic acid, aminosulfonic acid, and 2-hydroxy-4-methoxyphenylphenol-5-sulfonic acid.

[0023] The preparation method of the dual-agent etching solution composition comprises the following steps: uniformly mixing all components of the main agent; and uniformly mixing all components of the auxiliary agent.

[0024] Beneficial Effects

[0025] 1. The first etchant includes an organic acid and an inorganic acid, wherein the organic acid includes succinic acid, which can avoid etching defects such as two-segment corners, chamfers, cracks, top verticality, metal residues, etc., and meet the requirements of etching of Cu / MoNb films.

[0026] 2. The organic acid also includes malic acid and malonic acid, and the weight ratio of malonic acid, malic acid and succinic acid is limited to (0.8-1.2):(0.5-1):1, which is compatible with the etching of Cu / MoNb film and MTD / Cu / MoNb film.

[0027] 3. The second etchant includes at least two of acetic acid, formic acid, butyric acid, citric acid, glycolic acid, oxalic acid, malonic acid, malic acid, valeric acid, propionic acid, tartaric acid, gluconic acid, succinic acid, and fumaric acid, which can enhance the chelation effect and etch copper thickness in the range of

[0028] 4. The maximum copper load can reach 10Kppm, which can meet the etching of copper concentration of 1~12Kppm.

[0029] 5. The etching solution of the present application does not contain fluorine, thus avoiding damage to the underlying metal of the substrate and the etching machine, while reducing toxic effects. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 The etching effect of the etching solution composition of Example 1, the thickness of the MTD (molybdenum nickel titanium) / Cu (copper) / MoNb (molybdenum niobium) three-layer film is 200 / 3500 /

[0031] Figure 2 The etching effect of the etching solution composition of Example 1, the Cu / MoNb three-layer film thickness is 3000 /

[0032] Figure 3 The etching effect of the etching solution composition of Example 1, the Cu / MoNb three-layer film thickness is 3000 / Figure 4 The etching effect of the etching solution composition of Example 1, the thickness of the MTD / Cu / MoNb three-layer film is 200 / 6000 /

[0033] Figure 5 The etching effect of the etching solution composition of Example 1, the thickness of the MTD / Cu / MoNb three-layer film is 200 / 8000 /

[0034] Figure 6 The etching effect of the etching solution composition of Example 2, the thickness of the MTD / Cu / MoNb three-layer film is 200 / 3500 /

[0035] Figure 7 The etching effect of the etching solution composition of Example 2, the Cu / MoNb three-layer film thickness is 5500 /

[0036] Figure 8 The etching effect of the etching solution composition of Example 3, the thickness of the MTD / Cu / MoNb three-layer film is 200 / 3500 /

[0037] Fig. 9 The etching effect of the etching solution composition of Example 3, the thickness of the Cu / MoNb three-layer film is 6000 /

[0038] Fig.10 The etching effect of the etching solution composition of Example 3, the thickness of the Cu / MoNb three-layer film is 8000 / Fig.11 The etching effect of the etching solution composition of Example 3, the thickness of the MTD / Cu / MoNb three-layer film is 200 / 6000 /

[0039] Fig.12 The etching effect of the etching solution composition of Example 3, the thickness of the MTD / Cu / MoNb three-layer film is 200 / 8000 /

[0040] Fig.13The etching effect of the etching solution composition of Example 4, the thickness of the MTD / Cu / MoNb three-layer film is 200 / 3500 /

[0041] Fig.14 The etching effect of the etching solution composition of Example 4, the thickness of the MTD / Cu / MoNb three-layer film is 200 / 6000 /

[0042] Fig.15 The etching effect of the etching solution composition of Example 4, the thickness of the MTD / Cu / MoNb three-layer film is 200 / 8000 /

[0043] Fig.16 The etching effect of the etching solution composition of Example 5, the thickness of the MTD / Cu / MoNb three-layer film is 200 / 3500 /

[0044] Fig.17 The etching effect of the etching solution composition of Example 5, the thickness of the MTD / Cu / MoNb three-layer film is 200 / 6000 /

[0045] Fig.18 The etching effect of the etching solution composition of Example 5, the thickness of the MTD / Cu / MoNb three-layer film is 200 / 8000 /

[0046] Fig.19 The etching effect of the etching solution composition of Example 6, the thickness of the MTD / Cu / MoNb three-layer film is 200 / 3500 /

[0047] Fig. 20 The etching effect of the etching solution composition of Example 6, the thickness of the MTD / Cu / MoNb three-layer film is 200 / 6000 /

[0048] Fig.21 The etching effect of the etching solution composition of Example 6, the thickness of the MTD / Cu / MoNb three-layer film is 200 / 8000 /

[0049] Fig. 22 The etching effect of the etching solution composition of Example 7, the thickness of the MTD / Cu / MoNb three-layer film is 200 / 3500 /

[0050] Fig.23 The etching effect of the etching solution composition of Example 7, the thickness of the MTD / Cu / MoNb three-layer film is 200 / 6000 /

[0051] Fig.24 The etching effect of the etching solution composition of Example 7, the thickness of the MTD / Cu / MoNb three-layer film is 200 / 8000 /

[0052] Fig.25 The etching effect of the etching solution composition of Comparative Example 1 is shown in FIG. 1. The thickness of the MTD / Cu / MoNb three-layer film is 200 / 3500 /

[0053] Fig.26 The etching effect of the etching solution composition of Comparative Example 1 is shown in FIG. 1. The thickness of the Cu / MoNb three-layer film is 3000 / Fig. 27 The etching effect of the etching solution composition of Comparative Example 1 is shown in FIG. 1. The thickness of the MTD / Cu / MoNb three-layer film is 200 / 8000 /

[0054] Fig.28 The etching effect of the etching solution composition of Comparative Example 2 is shown in FIG. 1 . The thickness of the MTD / Cu / MoNb three-layer film is 200 / 3500 /

[0055] Fig.29 The etching effect of the etching solution composition of Comparative Example 2 is shown in FIG. 1 . The thickness of the Cu / MoNb three-layer film is 5500 /

[0056] Fig.30 The etching effect of the etching solution composition of Comparative Example 2 is shown in FIG. 1 . The thickness of the Cu / MoNb three-layer film is 3000 / DETAILED DESCRIPTION

[0057] Examples 1-7, Comparative Examples 1-2

[0058] A dual-component etching solution composition includes a main agent and an auxiliary agent, as shown in Table 1 by weight percentage:

[0059] Among the main agents, malonic acid, malic acid, citric acid, succinic acid and phosphoric acid are the first etching agents; isobutanolamine and isopropanolamine are the first inhibitors; 5-aminotetrazole, 3-amino-1,2,4-triazole, phenyl urea, ethylene glycol monobutyl ether and diethylene glycol monobutyl ether are the first stabilizers.

[0060] Among the auxiliary agents, malonic acid, malic acid and citric acid are the second etching agents; iminodiacetic acid is the chelating agent; 5-aminotetrazole, 3-amino-1,2,4-triazole, 5-methyltetrazole, isopropanolamine and phenolsulfonic acid are the second stabilizers; and isopropanolamine is the second inhibitor.

[0061] Table 1

[0062]

[0063]

[0064] The preparation method of the dual-agent etching solution composition comprises the following steps: uniformly mixing all components of the main agent; and uniformly mixing all components of the auxiliary agent.

[0065] Performance Testing Methods and Data

[0066] The etching solutions obtained in the examples and comparative examples were subjected to performance tests, and the etching conditions were as follows: the etching time was adjusted so that the single-side CD loss was ≤ 0.9 μm. The test data are listed in Table 2.

[0067] The specific method of using the etching composition for etching is as follows: first use the main etching agent, and for every 1000 ppm increase in copper ions, add 1.4 wt% of the main agent dosage of the auxiliary agent to the system.

[0068] Among them Figure 1-24 As shown, the etching solution prepared in the embodiment of the present application has a good etching effect on three-layer film and two-layer film, as well as on different copper thicknesses of 3500 / 6000 / 8000; during the etching process of the etching solution prepared in Comparative Example 1, Fig.26 The test piece has interface cracks and chamfers, and Fig.25 The test piece has copper chamfers. Fig. 27 The CD and taper of the test piece are low; Figure 28-30 As shown, the etching solutions prepared in Comparative Example 2 all have interface cracks.

[0069] Table 2

[0070]

Claims

1. A dual-component etching solution composition, characterized in that: The invention comprises a main agent and an auxiliary agent, wherein the main agent comprises, by weight percentage, 8-20% hydrogen peroxide, 1-10% first etchant, 1-10% first inhibitor, 0.1-5% first stabilizer, and the balance is made up by deionized water; the auxiliary agent comprises 5-30% second etchant, 0.1-5% second inhibitor, 1-10% chelating agent, 10-40% second stabilizer, and the balance is made up by deionized water; The first etchant includes an organic acid and an inorganic acid, and the organic acid includes succinic acid.

2. The dual-component etching solution composition according to claim 1, characterized in that: The organic acids also include malic acid and malonic acid.

3. The dual-component etching solution composition according to claim 2, characterized in that: The weight ratio of malonic acid, malic acid and succinic acid is (0.8-1.2):(0.5-1):

1.

4. The dual-component etching solution composition according to claim 3, characterized in that: The second etchant includes at least two of acetic acid, formic acid, butyric acid, citric acid, glycolic acid, oxalic acid, malonic acid, malic acid, valeric acid, propionic acid, tartaric acid, gluconic acid, succinic acid, and fumaric acid.

5. The dual-component etching solution composition according to claim 3, characterized in that: The weight ratio of the organic acid to the inorganic acid is (4-8):(0.1-0.2).

6. The dual-component etching solution composition according to claim 1, characterized in that: The first inhibitor and the second inhibitor are both selected from at least one of heterocyclic aromatic compounds and heterocyclic aliphatic compounds.

7. The dual-component etching solution composition according to claim 1, characterized in that: The first stabilizer includes an organic base, and the organic base includes at least one of phenylenediamine, dimethylaminopropylamine, isopropanolamine, diethanolamine, and triisopropanolamine.

8. The dual-component etching solution composition according to claim 7, characterized in that: The first stabilizer further comprises at least one of a thiourea stabilizer and an ether stabilizer.

9. The dual-component etching solution composition according to claim 1, characterized in that: The chelating agent includes at least one of glycine, iminodiacetic acid, alanine, glutamine, asparagine, lysine and arginine.

10. The dual-component etching solution composition according to claim 1, characterized in that: The second stabilizer includes at least one of phenolsulfonic acid, naphthalenesulfonic acid, p-toluenesulfonic acid, cresolsulfonic acid, dodecylbenzenesulfonic acid, and aminosulfonic acid.

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